The present invention relates to antimicrobial detergent compositions which can be used for the purpose of removal of microorganism and deodorization of washings and sterilization and antibacterialization etc. in food factories, hospitals etc. and more specifically relates to antimicrobial detergent compositions which can be used favorably as detergents and softeners used for washing, detergents for cleaning, detergents used for walls, floors etc. of food factories, hospitals etc.
Clothes, bed sheets etc. used in the clinical spots used to be contaminated with blood, fluid, fat etc. and further with pathogens, viruses etc. For these clothes, bed sheets etc. detergents containing bactericide should be used to conduct not only washing but also such treatments as sterilization, antibacterialization, removal of microorganism, deodorization etc. Moreover, in cleaning, a bactericide is used usually with detergents to prevent clothes from contamination and keep them in a hygienic condition.
Recently, perhaps from cleanliness-oriented tendency, removal of microorganism and odor of clothes, bed sheets etc. are conducted also at general household together with washing and therefore detergents, softeners etc. containing bactericide appear on the market. Among these antimicrobial agents for washing, however, there are antimicrobial agents which appear adaptation of bacteria when used for longer period of time and lose effects of removal of microorganism, deodorization etc.
Infection of drug-resistant bacteria such as MRSA (Methicillin-resistant Staphylococcus aureus) to weak inpatients in hospitals has become a big social problem and it is desired to use detergents containing bactericides, which do not produce drug-resistant bacteria, as detergents to be used for walls, floors etc. Moreover, the existence of not only drug-resistant bacteria but also bacteria themselves matters in food factories and therefore there are desired highly safe antimicrobial agents which not only produce no drug-resistant bacteria but also have a wide antimicrobial activity spectrum.
The object of the present invention is to provide a highly safe antimicrobial agent which not only produces no drug-resistant bacteria but also has a wide antimicrobial activity spectrum even in case it is used for a longer period of time contained in detergents, softeners, detergents for cleaning and detergents used for walls, floor etc. of food factories, hospitals etc.
The present inventors have been intensively studying to solve the above-mentioned problem. As a result, this time, they found that bis-quarternary ammonium compounds represented by the following general formula (I) are suitable to be used for a longer period of time contained in detergents, softeners, detergents for cleaning and detergents used for walls, floor etc. of food factories, hospitals etc. (in the present specification they are collectively called as xe2x80x9cdetergent compositionxe2x80x9d), because they are highly safe to human body and natural environment, have a wide antimicrobial activity spectrum, produce no drug-resistant bacteria even in case of use for a longer period of time, and show effects against MRSA at a low concentration and completed the present invention.
Thus, according to the present invention, there is provided an antimicrobial detergent composition characterized by containing, as an antimicrobial agent, at least one bis-quaternary ammonium compound of the general formula 
wherein the two R1 may be the same or different and each represent an alkyl group of 1 to 18 carbon atoms or an alkenyl group of 3 to 18 carbon atoms; the two R2 may be the same or different and each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group of 1 to 6 carbon atoms or an alkoxy group of 1 to 3 carbon atoms; R3 represents an alkylene group of 1 to 18 carbon atoms, an alkenylene group of 3 to 18 carbon atoms or a phenylene or xylylene group which may optionally be substituted by an alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 6 carbon atoms or an alkoxycarbonyl group of 2 to 6 carbon atoms; Y1 represents xe2x80x94NHCOxe2x80x94, xe2x80x94CONHxe2x80x94, xe2x80x94NHCSxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94COSxe2x80x94, xe2x80x94Oxe2x80x94 or xe2x80x94Sxe2x80x94; Y2 represents xe2x80x94CONHxe2x80x94, xe2x80x94NHCOxe2x80x94, xe2x80x94CSNHxe2x80x94, xe2x80x94OOCxe2x80x94, xe2x80x94SOCxe2x80x94, xe2x80x94Oxe2x80x94 or xe2x80x94Sxe2x80x94; and X represents anions.
The antimicrobial (i.e., antibacterial or antifungal) detergent compositions of the present invention will be more specifically described hereinbelow.
As used herein, the term xe2x80x9calkyl groupxe2x80x9d denotes a straight-chain or branched alkyl group, and examples thereof include methyl, ethyl propyl, isopropyl, butyl, isobutyl, sec-butyl pentyl, isopentyl, sec-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl isodecyl, dodecyl, tetradecyl, hexadecyl and octadecyl etc. From the viewpoint of antibacterial power, the alkyl groups represented by R1 are preferably ones having 8 or more carbon atoms.
The term xe2x80x9calkenyl groupxe2x80x9d denotes a straight-chain or branched alkenyl group, and examples thereof include allyl, methallyl, pentenyl hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl, etc.
The term xe2x80x9calkoxy groupxe2x80x9d denotes an alkyloxy group in which the alkyl moiety has the above-described meaning, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- butoxy and tert- butoxy.
The term xe2x80x9calkylene groupxe2x80x9d preferably denotes a group of the formula "Parenopenst"CH2"Parenclosest"n. In this formula, n is preferably in the range of 2 to 18 and more preferably 3 to 8.
The term xe2x80x9calkenylene groupxe2x80x9d comprehends, for example, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94 and xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94.
The term xe2x80x9calkoxycarbonyl groupxe2x80x9d denotes an alkyloxycarbonyl group in which the alkyl moiety has the above-described meaning, and examples thereof include methoxycarbonyl and ethoxycarbonyl.
The term xe2x80x9chalogen atomxe2x80x9d comprehends fluorine, chlorine, bromine and iodine.
The term xe2x80x9canionxe2x80x9d comprehends inorganic anions such as halogen ions (e.g., Clxe2x88x92, Brxe2x88x92 and Ixe2x88x92) and nitrate ion (NO3xe2x88x92); and organic acid anions such as acetate ion (CH3COOxe2x88x92) and propionate ion (C2H5COOxe2x88x92).
Among the compounds represented by the above formula (I), a preferred group of compounds are those of formula (I) in which the two R1 may be the same or different, and each represents an alkyl group of 8 to 18 carbon atoms; the two R2 may be the same or different, and each represents a hydrogen atom or a chlorine atom; R3 represents an alkylene group of 3 to 8 carbon atoms, a phenylene group or a xylylene group; Y1 represents xe2x80x94NHCOxe2x80x94, xe2x80x94CONHxe2x80x94, xe2x80x94COOxe2x80x94 or xe2x80x94Sxe2x80x94; Y2 represents xe2x80x94CONHxe2x80x94, xe2x80x94NHCOxe2x80x94, xe2x80x94OOCxe2x80x94 or xe2x80x94Sxe2x80x94; and X represents a halogen ion or an acetate ion.
Specific examples of the compounds of the above formula (I) used as antimicrobial agents in the composition of the present invention are as follows:
N,Nxe2x80x2-Hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) (xe2x80x9cDimer 38xe2x80x9d; manufactured by INUI CORPORATION),
N,Nxe2x80x2-hexamethylenebis(4-carbamoyl-1-decylpyridinium acetate) (xe2x80x9cDimer 38Axe2x80x9d; manufactured by INUI CORPORATION),
4,4xe2x80x2-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) (xe2x80x9cDimer 136xe2x80x9d; manufactured by INUI CORPORATION
4,4xe2x80x2-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium acetate) (xe2x80x9cDimer 136Axe2x80x9d; manufactured by INUI CORPORATION),
1,4-tetramethylenebis(4-carbamoyl-1-hexadecylpyridinium bromide),
1,6-hexamethylenebis(3-carbamoyl-1-dodecylpyridinium bromide),
1,8-octamethylenebis(3-carbamoyl-1-tetradecylpyridinium bromide),
3,3xe2x80x2-(1,3-trimethylenedicarbonyldiamino)bis(1-decylpyridinium bromide),
4,4xe2x80x2-(p-xylyldithio)bis(1-octylpyridinium iodide),
3,3xe2x80x2-(m-xylyldithio)bis( 1-tetradecylpyridinium bromide),
N, Nxe2x80x2-(p-phenylene)bis(4-carbamoyl-1-octylpyridinium bromide),
N,Nxe2x80x2-(m-phenylene)bis(3-carbamoyl-1-dodecylpyridinium bromide),
4,4xe2x80x2-(p -phthalamido)bis(1-octylpyridinium bromide),
3,3xe2x80x2-(m-phthalamido)bis(1-octadecylpyridinium iodide),
4,4xe2x80x2-(1,8-octamethylenedioxy)bis(1-dodecylpyridinium bromide),
3,3xe2x80x2-(1,6-hexamethylenedioxy)bis(1-hexadecylpyridinium bromide),
4,4xe2x80x2-(1,6-hexamethylenedioxydicarbonyl)bis(1-octylpyridinium bromide),
3,3xe2x80x2-(1,4-tetramethylenedioxydicarbonyl)bis(1-dodecylpyridinium bromide),
4,4xe2x80x2-(1,4-tetramethylenedicarbonyldioxy)bis(1-octylpyridinium bromide),
3,3xe2x80x2-(p-phthaloyldioxy)bis(1-decylpyridinium chloride),
4,4xe2x80x2-(1,8-octamethylenedicarbonyldithioxy)bis(1-octadecylpyridinium bromide) and
3,3xe2x80x2-(m-phthaloyldithioxy)bis(1-decylpyridinium iodide).
The compounds of the above formula (I) are disclosed, for example, in the publications of Japanese Laid- Open Patent Publication (KOKAI) Nos. 1106921/""97, 957731/""98, 287566/""98, P2000-95763A and P2000- 136185A, all of which were filed in the name of the present applicant or assignee, or may be prepared according to the processes described in these publications or specifications.
The compounds of the above formula (I) are extremely safe with low toxicity and little skin irritation.
The compounds of the above formula (I) can be used each singly or in combination of 2 kinds or more for detergents, softeners, detergents for cleaning and detergents used for walls, floor etc. of food factories, hospitals etc. or can be used together with other agents such as bactericides.
The antimicrobial detergent compositions of the present invention can be prepared in the entirely same procedure as usual detergent compositions, except compounding the compounds of the above formula (I) in the above detergent compositions. The mixed amount in the detergent composition varies according to the application purposes of the final detergent composition, kinds of antimicrobial agents etc. Generally, however, it is preferable in the range of 0.1-50% by weight, particularly 0.5-35% by weight, and more particularly 1-20% by weight, based upon the weight of the composition.
The detergents, in which the compounds of the above formula (I) can be mixed, are solid or liquid compositions comprising soap or other surfactants and containing as auxiliary components builder, foam-forming agent, fluorescent brightening agent, solvent, perfume etc. and include heavy duty detergent mainly used for cleaning of clothes, light duty detergent mainly used for kitchen, housing, shampoo etc.
As surfactants there can be used, for example, nonionic surfactants of ethylene oxide type, alkylphenol type and pluronic type, etc.
The antimicrobial detergent compositions of the present invention have excellent bactericidal, antimicrobial, bacteria-removal and/or deodoring effects and produce no drug-resistant bacteria even on using for longer period of time and therefore can be widely used, for example, for cleaning of clothes and other textile products, for domestic detergents, for cleaning within the facilities such as food factories, hospitals etc.